Bio-inspired Hydroxyapatite/Gelatin Transparent Nanocomposites

Hydroxyapatite(HA)nanoparticles impart outstanding mechanical properties to organicinorganic nanocomposites in bone.Inspired by the composite structure of HA nanoparticles and collagen in bone,a high performance HA/gelatin nanocomposite was first developed.The nanocomposites have much better mechanical properties(elongation at break 29.9%,tensile strength 90.7 MPa,Young’s modulus 5.24 GPa)than pure gelatin films(elongation at break 9.3%,tensile strength 90.8 MPa,Young’s modulus 2.5 GPa).In addition,the composite films keep a high transmittance in visible wavelength range from 0%to 60%of the HA solid content.These differences in properties are attributed to the homogeneous distribution of HA nanoparticles in the gelatin polymer matrix and the strong interaction between the particle surfaces and the gelatin molecules.This protocol should be promising for HA-based nanocomposites with enhanced mechanical properties for biomedical applications.

Ionic liquid-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid

The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali,we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance.The results showed that the ionic liquid[Bmim]BF_(4) can affect the crystal growth of hydroxyapatite,provide fluoride ion for fluorination of hydroxyapatite,and adjust the surface acidity and basicity,morphology,textural properties,crystallinity,and composition of hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows:a mass ratio of[Bmim]BF4 to calcium salt=0.2:1,a hydrothermal time of 12 h,and a hydrothermal temperature of 130℃.A maximal methacrylic acid yield of 54.7%was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions(250℃ and 2 MPa of N_(2))in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

Effect of Fluoride on the Ion-association of Calcium Phosphate and Crystallization of Hydroxyapatite

Using a titration setup to accurately control the reaction conditions and in situ monitor the reaction,we showed that fluoride exhibited negligible effects on the ion association process of calcium and phosphate and the formation of ACP nanospheres in a buffer solution with constant ionic strength.However,the stability of ACP increased with increasing fluoride concentration,which was ascribed to the inhibitory effect of fluoride on the aggregation of ACP nanospheres and the nucleation of nanocrystals on the surface of ACP nanospheres.Furthermore,fluoride could inhibit the lateral growth of HAP nanosheets and promote the formation of rod-like crystals.These results further improve our understanding of the crystallization pathway of HAP crystals and the regulatory effects of fluoride.

Influence of anodization conditions on deposition of hydroxyapatite onα/βTi alloys for osseointegration:Atomic force microscopy analysis

Integrating titanium-based implants with the surrounding bone tissue remains challenging.This study aims to explore the impact of different anodization voltages(20−80 V)on the surface topography of two-phase(α/β)Ti alloys and to produce TiO_(2) films with enhanced bone formation abilities.Scanning electron microscopy coupled with energy dispersive spectroscopy(SEM−EDS)and atomic force microscopy(AFM)were applied to investigate the morphological,chemical,and surface topography of the prepared alloys and to confirm the growth of hydroxyapatite(HA)on their surfaces.Results disclosed that the surface roughness of TiO_(2) films formed on Ti−6Al−7Nb alloys was superior to that of Ti−6Al−4V alloys.Ti−6Al−7Nb alloy anodized at 80 V had the highest yields of HA after immersion in simulated body fluid with enhanced HA surface coverage.The developed HA layer had a mean thickness of(128.38±18.13)μm,suggesting its potential use as an orthopedic implantable material due to its promising bone integration and,hence,remarkable stability inside the human body.

Characterization of Hydroxyapatite Extracted from Crab Shell Using the Hydrothermal Method with Varying Holding Times

Hydroxyapatite(HA)is a bio ceramic commonly utilized in bone tissue engineering due to its bioactive and osteoconductive properties.Crab shells are usually disregarded as waste material despite their significant CaCO_(3) content,and have not been widely utilized in the synthesis of HA.This study aims to synthesize and analyze HA derived from crab shells using the hydrothermal method with different durations of holding time.This study utilized precipitated calcium carbonate(PCC)derived from crab shells.With a hydrothermal reactor set at 160℃ and varying holding times of 14(HA_14),16(HA_16),and 18(HA_18)h,a PCC and(NH4)2HPO4 mixture was used to synthesize HA.The synthesis results were analyzed using scanning electron microscopy(SEM),fourier transform infrared spectroscopy(FTIR),and X-ray diffraction(XRD)tests.This study has accomplished the synthesis of HA from crab shells.Nonetheless,the final product of synthesis still contained CaCO_(3) as an impurity.The prolonged hydrothermal holding time of 14 to 18 h resulted in a reduction of impurities while increasing the percentage of crystal weight and crystallite size of HA.Specimen CH_18 is the best-quality product generated in this study.This specimen produced HA with the highest percentage of crystal weight and crystallite size compared to the other specimens.Furthermore,specimen CH_18 exhibited the lowest concentration of impurities.The Ca/P ratio in this specimen was also the closest to 1.67.The Ca/P ratio,crystallite size,and crystal weight percentage of this specimen are 1.54,19.06 nm,and 99.1%,respectively.

Flexoelectricity in hydroxyapatite for the enhanced piezocatalytic degradation of phenanthrene in soil

Coupling the effects of flexoelectricity with piezoelectricity has been proved to effectively harvest mechanical energy.In this study,a composition-graded core–shell structure(HAP@FAP)was prepared by surface-gradient F-doping in hydroxyapatite,which could introduce flexoelectricity by a built-in strain gradient.A flexoelectric-boosted piezoelectric response was demonstrated by piezoresponse force microscopy(PFM)characterization,showing that the piezoelectric constant of HAP@FAP was increased by 2.25 times via a lattice strain gradient induced by chemical heterogeneities derived from the unique composition-graded core-shell structure.Thus,the piezocatalytic activity of HAP@FAP for phenanthrene(PHE)degradation in soil was enhanced.This work provides a new strategy for the modification of piezoelectric catalysts for the remediation of organics-contaminated soils on industrial land.

Effect of cetyltrimethylammonium bromide on morphology and porous structure of mesoporous hydroxyapatite

The mesoporous hydroxyapatite （HA） was synthesized by hydrothermal method utilizing cationic surfactant cetyltrimethylammonium bromide （CTAB） as template. The crystalline phase, morphology and porous structure were characterized respectively by different detecting techniques. The results reveal that the particles are highly crystalline hydroxyapatite phase. The surfactant has little influence on the morphology of the crystals, but affects the porous structure obviously. The sample without CTAB has a low surface area not exceeding 33 m^2/g, and no distinct pores can be observed by TEM. While the samples obtained with the surfactant get better parameters. Numerous open-ended pores centered at 2-7 nm spread unequally on the surface of the hydroxyapatite nanorods. The N2 adsorption-desorption experiments show type IV isotherms with distinct hysteresis loops, illustrating the presence of mesoporous structure. When the mole ratio of CTAB to HA is 1：2, the sample has the largest surface area of 97.1 m^2/g and pore volume of 0.466 cm^3/g.

Arginine functionalized hydroxyapatite nanoparticles and its bioactivity for gene delivery

In order to further improve the transfection efficiency of hydroxyapatite nanoparticle （HAp）, arginine functionalized hydroxyapatite （HAp/Arg） was synthesized by hydrothermal synthesis. The morphology, crystallite size and zeta potential of the HAp/Arg were characterized by transmission electron microscopy （TEM）, atomic force microscopy （AFM） and zeta potential analyzer. The loading and protecting properties of HAp/Arg to DNA were tested by electrophoresis. Its cytotoxicity was also measured in Hela cells and HAEC cells by MTT and LDH, and its transfection efficiency was examined by fluorescence microscope and flow cytometry. The results reveal that HAp/Arg is short rod-like and nano single crystal, the mean diameter is 50-90 nm and zeta potential is 35.8 mV at pH 7.4. HAp/Arg to DNA can be condensed by electrostatic effect and protect DNA against degradation in DNase I, and shows high transfection efficiency without cytotoxicity. These results suggest that HAp/Arg can be a promising alternative as a novel gene delivery system.

Synthesis of Crystalline Hydroxyapatite from CaCO_3 and CaHPO_4·2H_2O by Mechanochemical Method

The mixture of CaHPO 4·2H 2O and CaCO 3 was ground in an aqueous system under appropriate conditions to investigate the mechanochemical reaction for the synthesis of crystalline hydroxyapatite (HA) powder. Hydroxyapatite of high crystallinity powder including trace Ca 10 (PO 4) 6CO 3(OH) and Ca 9HPO 4(PO 4) 6OH can be synthesized by mechanical activation without further thermal treatment at a high temperature. The synthesis reaction during the grinding process was almost completed within 1h. The as-ground powder exhibits a particle distribution of 20-100nm in size with a spherical or rodlike morphology. The composition and degree of crystallinity of the mechanochemical synthesized hydroxyapatite powders were coincident with the cement-type hydroxyapatite.

Synthesis and characterization of arginine-modified and europium-doped hydroxyapatite nanoparticle and its cell viability

The arginine-modified and europium-doped hydroxyapatite nanoparticles（HAP-Eu） were synthesized by hydrothermal synthesis.The prepared nanoparticles were characterized by transmission electron microscopy（TEM）,X-ray diffractometry（XRD）,Fourier transform infrared（FTIR） and zeta potential analyzer.The cell viability of HAP-Eu was tested by image flow cytometry.The results indicated that HAP-Eu is short column shapes and its size is approximately 100 nm,its zeta potential is about 30.10 mV at pH of 7.5,and shows no cytotoxicity in human epithelial cells and endothelial cells.

Effects of Nanometer Hydroxyapatite on Proliferation of Periodontal Ligament Fibroblasts

Objective:To investigate possible effects of nanophase powder of hydroxyapatite on proliferation of periodontal ligament cells. Methods: With sol-gel method, the nanophase hydroxyapatite powders were fabricated. These powders were proved nanopaticles by transmission electron microscope. The effects on proliferation of periodontal ligament cell(PDLC) were observed in vitro with MTT [3-(4,5dimethylthiazo;-2-yl)-2,5-diphenytetralium bromide] method. Results: On the 2nd,3rd,4th day after treated with nanoparticles of hydroxyapatite, the proliferate activity of the PDLC increases significantly, compared with those with dense hydroxyaoatite and control but no significant difference could be found between the dense hydroxyapatite and the control. Conclusion: Nanophase hydroxyapatite can promote the regeneration of periodontal tissue.

In-vitro degradation behavior of Mg alloy coated by fluorine doped hydroxyapatite and calcium deficient hydroxyapatite

Fluorine-doped hydroxyapatite(FHA) and calcium deficient hydroxyapatite(CDHA) were coated on the surface biodegradable magnesium alloy using electrochemical deposition(ED) technique. Coating characterization was investigated X-ray diffraction(XRD), Fourier-transformed infrared spectroscopy(FTIR), transmission electron microscopy(TEM), scanni electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDS). The result shows that nano-FHA coated samp presents nano needle-like structure, which is oriented perpendicular to the surface of the substrate with denser and more unifo layers compared to the nano-CDHA coated sample. The nano-FHA coating shows smaller crystallite size(65 nm) compared to t nano-CDHA coating(95 nm); however, CDHA presents thicker layer(19 μm in thickness) compared to the nano-FHA(15 μm thickness). The corrosion behaviour determined by polarization, immersion and hydrogen evolution tests indicates that the nano-FH and nano-CDHA coatings significantly decrease corrosion rate and induce passivation. The nano-FHA and nano-CDHA coatings c accelerate the formation of bone-like apatite layer and significantly decrease the dissolution rate as compared to the uncoated M alloy. The nano-FHA coating provides effective protection to Mg alloy and presents the highest corrosion resistance. Therefore, t nano-FHA coating on Mg alloy is suggested as a great candidate for orthopaedic applications.

Effects of Pb^(2+), Cd^(2+) and Cu^(2+) on the Aqueous Zn^(2+) Sorption by Hydroxyapatite

In this paper, the behaviors of aqueous zinc sorption by hydroxyapatite in the co-existence of Pb^2＋, Cd^2＋ and Cu^2＋ are investigated, the effects of Pb^2＋, Cd^2＋ and Cu^2＋ on the sorption of Zn^2＋ are discussed, and the hydroxyapatite sorption capabilities for Pb^2＋, Cd^2＋, Cu^2＋ and Zn^2＋ are compared. The experimental results show that the Zn^2＋ removal efficiency decreases gradually with the increase of the Cd^2＋ concentration of the solution, and there is no sorption preference between Cd^2＋ and Zn^2＋. On the other hand, the Zn^2＋ removal efficiency rapidly decreases rapidly with the increase of the Cu^2＋ concentration of the solution, and there is a clear sorption preference between Cu^2＋ and Zn^2＋. It is noticed that the Zn^2＋ removal efficiency is hardly changed with the variance of Pb^2＋ concentration because the removal mechanisms for these two ions are totally different. It is concluded that the adsorption affinities of the heavy metals for the hydroxyapatite follows this sequence： pb^2＋〉 Cu^2＋〉 Cd^2＋〉 Zn^2＋.

Preparation of Hydroxyapatite Cement and Analysis as of its Disposition

Objective: To prepare hydroxyapatite cement (or calcium phosphate cement, CPC) and analyze its capability. Methods: Tetracalcium phosphate (TTCP) was prepared by the method of high heat. TTCP reacted with in simulated body situation and produced CPC, Its capability was analyzed by scanning electron microscopy (SEM) , X-ray diffraction(XRD). Its density, absorbing water coefficient, macroporosity and campressive strength were measured also. Results: The main element of CPC is hydroxyapatite (HA) , its microstructure comprised of needlelike or petal crystals. The diameter of micropore was 4-10 nm, density was 1.922 g/cm3, macroporosity was 29. 777% , absorbing coefficient was 15. 503%, compressive strength was 42. 70 Mpa. Conclusion: This CPC has three-dimensional spatial structure, its strength meets the need of cancellous bone grafting.

Biologically Inspired Self-assembling Synthesis of Bone-like Nano-hydroxyapatite/PLGA-(PEG-ASP)_n Composite: A New Biomimetic Bone Tissue Engineering Scaffold Material

A new biomimetic bone tissue engineering scaffold material, nano-HAI PLGA-（ PEG-Asp ）n composite, was synthesized by a biologically inspired self-assembling approach. A novel biodegradable PLGA- （ PEG-Asp ）n copolymer with pendant amine functional groups and enhanced hydrophilicity woo synthesized by bulk ring-opening copolymerization by DL-lactide（ DLLA） and glycolide（ GA ） with Aspartic acid （ Asp ）-Polyethylene glycol（PEG） alt-prepolymer. A Three-dimensional, porous scaffold of the PLGA-（ PEG- Asp）n copolymer was fabricated by a solvent casting , particulate leaching process. The scaffold woo then incubated in modified simulated body fluid （naSBF）. Growth of HA nanocrystals on the inner pore surfaces of the porous scaffold is confirmed by calcium ion binding analyses, SEM , mass increooe meoourements and quantification of phosphate content within scaffolds. SEM analysis demonstrated the nucleation and growth of a continuous bonelike, low crystalline carbonated HA nanocrystals on the inner pore surfaces of the PLGA- （ PEG-Asp ）n scaffolds. The amount of calcium binding, total mass and the mass of phosphate on experimental PLGA- （ PEG-Asp ） n scaffolds at different incubation times in mSBF was significantly greater than that of control PLGA scaffolds. This nano-HA/ PLGA-（ PEG- Asp ）n composite stunts some features of natural bone both in main composition and hierarchical microstrueture. The Asp- PEG alt-prepolymer modified PleA copolymer provide a controllable high surface density and distribution of anionic functional groups which would enhance nucleation and growth of bonelike mineral following exposure to mSBF. This biomimetic treatment provides a simple method for surface functionalization and sabsequent mineral nucleation and self-oosembling on bodegradable polymer scaffolds for tissue engineering.

Advances in hydroxyapatite coatings on biodegradable magnesium and its alloys

Magnesium is a candidate metal for biodegradable implant applications for its biodegradation tendency and excellent biocompatibility.Unfortunately,the high degradation rate of magnesium and also its localized degradation in physiological conditions are the main issues for its successful implant applications.The degradation rate of magnesium has been reduced to some degree via alloying,but the localized degradation susceptibility is a great concern.For many years,hydroxyapatite(HAp),a biocompatible ceramic material,has been extensively used for bio-implant applications.Recently,a substantial amount of research has been carried out on coating HAp on magnesium-based materials for improved degradation resistance in particular and also to enhance the biocompatibility.This review article focuses on the different methods of HAp coating on magnesium-based materials and also the recent cutting-edge advancements made in the coating process for improved degradation resistance and biocompatibility.The mechanical stability of the HAp coated magnesium-based materials is also discussed.

Cytotoxinic Mechanism of Hydroxyapatite Nanoparticles on Human Hepatoma Cell Lines

Stable and single dispersed HAP nanoparticles were synthesized with chemical method assisted by ultrasonic treatment.HAP nanoparticles were surveyed by AFM and Zataplus.The effect on the Bel-7402 human hepatoma cell lines treated with HAP nanoparticles was investigated by the MTT methods and observation of morphology,and the mechanism was studied in changes of cell cycle and ultrastructure.The result shows that inhibition of HAP nanoparticles on the Bel 7402 human hepatoma cell lines is obviously in vitro.HAP nanoparticles the entered cancer cytoplasm,and cell proliferation is stopped at G 1 phase of cell cycle,thus,cancer cells die directly.

Preparation, Characterization and Antibacterial Property of Cerium Substituted Hydroxyapatite Nanoparticles

Nanoparticles of hydroxyapatite （HAP） and cerium substituted hydroxyapatite （CeHAP） with the atomic ratio of Ce/[ Ca ＋ Ce] （xco） from 0 to 0.2 were prepared by sol-gel-supercritical fluid drying （SCFD） method. The nanoparticles were characterized by TEM, XRD, and FT-IR, and the effects of cerium on crystal structure, crystallinity, and particle shape were discussed. With the tests of bacterial inhibition zone and antibacterial ratio, the antibacterial property of HAP and CeHAP nanoparticles on Escherichia coli, Staphylococcus aureus, Lactobacillus were researched. Results showed that the nanoparticles of HAP and CeHAP could be made by sol-gel-SCFD, cerium could partially substitute for calcium and enter the structure of HAP. After substitution, the crystallinity, the IR wavenumbers of bonds in CeHAP decreased gradually with increase of cerium substitution, and the morphology of the nanoparticles changed from the short rod-shaped HAP to the needle-shaped CeHAP. The nanoparticles of HAP and CeHAP with Xco below 0.08 had antibacterial property only forcibly contacting with the test bacteria at the test concentration of 0.1 g · mi^-1, however, the Ce- HAP nanoparticles had antibacterial ability at that concentration no matter statically or dynamically contacting with the test bacteria when Xco was above 0.08, and the antibacterial ability gets better with the increase Of Xce, indicating that the antibacterial property was improved after calcium was partially substituted by cerium. The improved antibacterial effects of CeHAP nanoparticle on Lactobacillus showed its potential ability to anticaries.

Improving the Corrosion Resistance of ZEK100 Magnesium Alloy by Combining High-Pressure Torsion Technology with Hydroxyapatite Coating

Recently,magnesium and its alloys have attracted more and more attention as promising implant materials due to their excellent properties such as good biocompatibility,biodegradation,non-toxicity and comparable mechanical properties with natural bone.They can be gradually degraded and absorbed so as to avoid the second surgery for implants removal after the tissues are healed completely.In addition,they are also able to prevent the stress shielding effect in human body environment because of the density,elastic modulus and yield strength of magnesium closer to the bone.Unfortunately,the high corrosion rate which causes early mechanical failure of the implants in physiological environment limits the widespread use of magnesium alloys for clinical application in biology.And the high corrosion process usually causes huge hydrogen evolution and alkalinization,resulting in problems against the implants as well as the surrounding tissues.In order to enhance the corrosion resistance of magnesium alloys,in this study,the ZEK100 magnesium alloy was pre-deformed with a highpressure torsion(HPT)process and then fabricated hydroxyapatite(HA)coatings with different contents of Mg(OH)2 nanopowder via hydrothermal method.The specimens were characterized by scanning electron microscope(SEM)and X-ray diffraction(XRD).At the same time,prior and after the HPT procedure,the metallography,microhardness and tensile tests of specimens were characterized.Meanwhile,the corrosion behavior of the specimens was evaluated by electrochemical impedance spectroscopy(EIS)and hydrogen evolution tests.And the interface bonding strength of the HA coating on the magnesium alloy substrate was evaluated by a tape adhesion test/scratch test.Results showed that HPT processing refined the grain size and introduced a great number of twins,resulting in the enhancement of microhardness and Young’s modulus of ZEK100 magnesium alloy,but hardness values at the edge were higher than those at the center due to the uneven shear strain.At the same conditions,the HA coating on HPT-ZEK was denser,thicker than that on ZEK sample and the crystal sizes of HA were smaller on HPT-ZEK.These were attributed to fine,uniform distributed secondary phases and lots of fine grains,twins,grain boundaries in HPT-ZEK substrates which can provide more nucleation sites for the HA crystal.In terms of the amount of Mg(OH)2 nanopowder,Mg(OH)2 nanopowder significantly influenced the microstructure and thickness of the HA coating.And at a 0.3 mg/mL content of Mg(OH)2 nanopowder,there was the densest,thickest HA coating on magnesium alloys,and the crystal size of HA was minimum.Specifically,the HA coating thickness on ZEK-03(0.3 mg/mL Mg(OH)2 nanopowder)was 1.8 times of that on ZEK-00(0 mg/mL Mg(OH)2 nanopowder),while the HA coating thickness on HPT-03 was 2.6 times of that on ZEK-00.And the adhesion strength of HA coating on HPT-03 substrate was better than that on ZEK-03.In addition,HPT technology and surface modification by HA coating simultaneously increased the corrosion resistance of ZEK100 magnesium alloy and the corrosion of HPT-ZEK samples occurred in a more uniform manner,while it was pitting on the surface of ZEK100 magnesium alloy.Therefore,there was the best corrosion resistance on HPT-03 sample,which could promote the application of magnesium alloys in biomedical fields.

Hydroxyapatite Bioceramic Coatings Prepared by Hydrothermal-electrochemical Deposition Method

The hydroxyapatite（HA） ceramic coating was successfully prepared on Ti6A14V alloy by the hydrothermal-electrochemical deposition method with constant voltage model. The phases of deposits were analyzed by X-ray diffraction. The releationship between crystallinity and depositing temperature was discussed. The microstructures of hydroxyapatite coating were observed by scanning electron microscope. The experimental results showed that the phases, crystaUinity and morphologies of deposits were influenced by depositing temperature （100℃, 120℃, 140℃, 160℃, 180℃ and 200℃, respectively）. The special hydrothermal environment can lower the crystallization temperature of HA. The crystallinity of HA increases firstly and then decreases with the increase of temperature. There is little hydroxyapatite deposited on the Ti6A14V surface when the depositing temperature is 100℃. The HA deposition increases with the increase of the depositing temperature. And the HA morphologies are influenced by the depositing temperature.